EP0340971B1 - Attractants for the Mediterranean fruit fly - Google Patents

Attractants for the Mediterranean fruit fly Download PDF

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Publication number
EP0340971B1
EP0340971B1 EP89304244A EP89304244A EP0340971B1 EP 0340971 B1 EP0340971 B1 EP 0340971B1 EP 89304244 A EP89304244 A EP 89304244A EP 89304244 A EP89304244 A EP 89304244A EP 0340971 B1 EP0340971 B1 EP 0340971B1
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EP
European Patent Office
Prior art keywords
composition
trans
fruit fly
mediterranean fruit
tml
Prior art date
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Expired - Lifetime
Application number
EP89304244A
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German (de)
English (en)
French (fr)
Other versions
EP0340971A3 (en
EP0340971A2 (en
Inventor
Terrence P Mcgovern
Roy T Cunningham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
United States Department of Commerce
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United States Department of Commerce
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/15—Saturated compounds containing halogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof

Definitions

  • This invention relates to novel attractants for the Mediterranean Fruit Fly, Ceratitis capitata Wiedmann, hereinafter referred to as the "Medfly.” More particularly, the present invention relates to novel isomeric blends of aliphatic esters of iodo- trans -2-methylcyclohexanecarboxylic acid, the method of their preparation and the method of use thereof to attract the Medfly for prolonged periods of time.
  • TML is the "standard" attractant most widely used in traps for survey and detection of the Medfly.
  • TML evaporates rapidly during hot weather thereby necessitating frequent and costly rebaiting of the traps. Further, the short residual life of TML (as well as Medlure and Siglure) mitigates against the development of an economical male-annihilation formulation of attractant plus insecticide.
  • TML also forms crystals during cold-weather storage so that the amount of the attractant is reduced in the supernatant. Because these crystals do not readily redissolve, special storage problems can occur in large volume programs.
  • An object of this invention is to provide novel attractants which are highly attractive to the Medfly for prolonged periods of time.
  • Another object of this invention is to provide persistent Medfly attractants which are comparable in attraction with TML but do not possess the deficiencies associated with TML.
  • one embodiment of the invention provides a composition to attract the Mediterranean Fruit Fly, comprising an attractant having an effective amount of a compound of the formula.
  • -CH3 and -COOR are in the trans -configuration and iodo atom is equatorial; and R is an ethyl, 2,2,2-trifluoroethyl, propyl, 1-methylethyl, 1-methyl-2, 2,2-trifluoroethyl.
  • the invention also provides a composition to attract the Mediterranean Fruit Fly comprising an attractant having an effective amount of a mixture of compounds of the formulae wherein -CH3 and -COOR are in the trans -configuration and the iodo atom is equatorial; R is as defined above and R in each of the formulae is identical.
  • the invention further provides a composition to attract the Mediterranean Fruit Fly, comprising an attractant having an effective amount of a mixture of compounds of the formulae wherein -CH3 and -COOR are in the trans -configuration and the iodo atom is equatorial and axial, but is more than 50% equatorial; R is as defined above; and R in each of the formulae is identical.
  • the term "4 and 5" is used herein to designate a mixture of the 4- and 5-iodo isomers wheren the iodo atoms of the invention esters are in both an equatorial and axial conformation, thus providing a blend of four stereoisomers for each ester.
  • esters useful in the present invention may be prepared as follows: The corresponding trans -6-methyl-3-cyclohexenecarboxylic acid (as prepared by a Diels-Alder reaction) is heated in a pressure vessel for 3 to 6 hours at elevated temperatures with aqueous hydriodic acid in the presence of an organic solvent, such as dioxane.
  • the resultant iodo- trans -2-methylcyclohexanecarboxylic acid is a mixture of the 4- and 5-iodo isomers and is converted to the corresponding acid halide by reacting with a suitable halogenating agent, such as thionyl chloride, phosphorus trichloride or phosphorus tribromide, under mild conditions, preferably at room temperature.
  • a suitable halogenating agent such as thionyl chloride, phosphorus trichloride or phosphorus tribromide
  • the acid halide is then reacted with the appropriate alcohol in a suitable solvent such as benzene or anhydrous ethyl ether in the presence of a hydrochloric acid scavenger such as pyridine, to yield the ester.
  • Isolation of the ester is accomplished by sequentially washing the crude reaction mixture with dilute acid, dilute base and saturated salt solutions. The crude product is thereafter dried over a suitable drying agent, filtered and the solvent removed. Final purification is accomplished by fractional distillation under high vacuum. Individual stereoisomers of the esters can be separated by high-performance liquid chromotography.
  • the stereoisomeric content of the esters can be easily varied by changing the reaction temperature during preparation of the ester.
  • invention esters synthesized by the addition of hydrogen iodide to the Diels-Alder acid adduct at moderately elevated temperatures, i.e. from 65°C to 80°C consist of a isomeric blend which has isomers A1 and A2 as it major components, with isomers B1 and B2 comprising 10% to 20% of the blend.
  • Esters synthesized by the addition of hydrogen iodide to the Diels-Alder acid adduct at 95°C to 130°C consist of an isomeric blend which consists of greater than 50% of isomers B1 and B2. Consequently, the higher the temperature the greater the B1/B2 isomer content in the resulting ester.
  • the most attractive isomer is B1 having an equatorial iodo atom attached at the 5 carbon atom.
  • B1 equatorial iodo atom attached at the 5 carbon atom.
  • the blend comprises an isomer content of from 50% to 100% of isomer B1 and B2 with isomers A1 and A2 comprising from 0% to 50% of the blend.
  • the esters may be used as is or they may be dissolved in volatile inert solvents such as liquid hydrocarbons, emulsified in water, or admixed with any other solid or inert liquid carrier.
  • volatile inert solvents such as liquid hydrocarbons, emulsified in water, or admixed with any other solid or inert liquid carrier.
  • the compounds When used in actual practice in the field, the compounds may be impregnated on a solid carrier such as paper, cloth, sawdust, wood chips, or other absorbent material.
  • the attractants may also be dispersed into the atmosphere by spraying or by dipping wicks into containers holding the ester composition. Further, the attractants may be used in bait traps usually provided with means to prevent the exit of insects so that the size and location of infestations may be ascertained.
  • the esters of the invention should be used in a substantially pure form, that is, the esters must be free of undesirable contaminants that tend to mask or otherwise inhibit their effectiveness as an attractant. It is within the compass of the invention to use the esters either individually or in combination.
  • the invention esters may also be used with other Medfly attractants or control agents, such as insecticides, chemosterilants or the like. When used, however, these agents should be used in an amount which, as readily determined by one skilled in the arts, will not interfere with the effectiveness of the invention esters.
  • the released organic acid was taken up in ether and was washed 3 times with water, then with dilute sodium bisulfite solution, again with water, dried over anhydrous magnesium sulfate and filtered. After removal of the solvent the crude iodo acid (ca 36 g) was used directly in the acid chloride synthesis. 26.8 g of the iodo acid (0.1 mole) was dissolved in 25 ml of benzene and 9 ml of thionyl chloride (0.125 mole) was added dropwise at room temperature. The reaction mixture was stirred overnight and the excess thionyl chloride and benzene were removed under vacuum with slight warming (40 °C).
  • the crude acid chloride was added dropwise to an excess of ethanol (12 ml) and 8 ml of pyridine in anhydrous ether. After standing overnight, the reaction mixture was extracted sequentially with water, dilute aqueous hydrochloric acid and sodium hydroxide and finally with saturated salt solution. After drying over anhydrous magnesium sulfate, the crude product was isolated and purified by fractional distillation under high vacuum, b.p. 81 °C/0.15mm Hg, recovered yield 15.0 g, approximately 67% of which consisted of isomers B1 and B2 and 33% of isomers A1 and A2 (from gc peak height measurement). If the product darkens excessively after distillation, the excessive color can be removed by washing the product with dilute sodium bisulfite solution.
  • the TML used in the tests was obtained commercially from UOP in East Rutherford, N.J.
  • Medfly captures obtained with fresh and aged TML was compared to captures obtained using the ethyl ester having the following isomeric content: (1) high A1 and A2, that is, more than 50% of isomers A1 and A2; (2) isomer A2; (3) isomers B1 and B2; (4) isomer B1 and (5) isomer B2 with ca. 2.5% of isomer B1.
  • the bioassay was the same as described in Example 4 except that a freshly baited TML wick was added to the test prior to each fly release and medflies were released at 0, 1, 3, 4, 8, 9, 10, 11 and 14 days postreatment.
  • Table II shows that of the four stereoisomers of the ethyl ester, the most attractive isomer was the B1 isomer. Traps with the B1 isomer had higher mean catches than those of fresh TML in the first 6 test periods and in 7 of the 9 test periods overall. Medfly captures with blends comprising the B1 isomer were significantly as attractive as fresh TML up to 10 days. All isomeric mixtures of the ethyl ester tested were more persistant than aged TML which began to fail between days 1 and 3.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP89304244A 1988-04-27 1989-04-27 Attractants for the Mediterranean fruit fly Expired - Lifetime EP0340971B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US186990 1988-04-27
US07/186,990 US4891217A (en) 1987-04-27 1988-04-27 Persistant attractants for the mediterranean fruit fly, the method of preparation and method of use

Publications (3)

Publication Number Publication Date
EP0340971A2 EP0340971A2 (en) 1989-11-08
EP0340971A3 EP0340971A3 (en) 1991-09-11
EP0340971B1 true EP0340971B1 (en) 1994-01-19

Family

ID=22687160

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89304244A Expired - Lifetime EP0340971B1 (en) 1988-04-27 1989-04-27 Attractants for the Mediterranean fruit fly

Country Status (10)

Country Link
US (1) US4891217A (ja)
EP (1) EP0340971B1 (ja)
JP (1) JPH06681B2 (ja)
AU (1) AU612846B2 (ja)
BR (1) BR8907401A (ja)
CA (1) CA1317219C (ja)
ES (1) ES2061985T3 (ja)
IL (1) IL90008A (ja)
PT (1) PT90367B (ja)
WO (1) WO1989010055A1 (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728394A (en) * 1994-12-12 1998-03-17 Photodye International, Inc. Pesticide composition and method for controlling the oriental fruit fly
US6375943B1 (en) 2000-01-14 2002-04-23 The United States Of America As Represented By The Secretary Of Agriculture Attractant for the mediterranean fruit fly, the method of preparation and method of use
DE102005015446A1 (de) * 2005-04-05 2006-10-12 Merck Patent Gmbh Synergisten zur Verstärkung der Wirkung von Repellentien

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3016329A (en) * 1959-08-06 1962-01-09 Beroza Morton Attractants for the male mediterranean fruit fly
US4152422A (en) * 1978-02-03 1979-05-01 The United States Of America As Represented By The Secretary Of Agriculture Attractant for male Mediterranean fruit fly
US4764366A (en) * 1987-04-27 1988-08-16 The United States Of America As Represented By The Secretary Of Agriculture Persistent attractants for the mediteranean fruit fly, the method of preparation and method of use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Journal of Economic Entomology, vol. 80, no. 3, p. 617-620 (1987) *

Also Published As

Publication number Publication date
IL90008A0 (en) 1989-12-15
WO1989010055A1 (en) 1989-11-02
JPH03502581A (ja) 1991-06-13
IL90008A (en) 1994-10-21
CA1317219C (en) 1993-05-04
ES2061985T3 (es) 1994-12-16
EP0340971A3 (en) 1991-09-11
BR8907401A (pt) 1991-04-23
EP0340971A2 (en) 1989-11-08
PT90367B (pt) 1991-10-31
AU612846B2 (en) 1991-07-18
JPH06681B2 (ja) 1994-01-05
US4891217A (en) 1990-01-02
AU3578389A (en) 1989-11-24

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